Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
  • H01M8/1018—Polymeric electrolyte materials
  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/0204—Polyarylenethioethers
  • C08G75/0286—Chemical after-treatment
  • C08G75/0295—Modification with inorganic compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0289—Means for holding the electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
  • H01M8/1018—Polymeric electrolyte materials
  • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
  • H01M8/1086—After-treatment of the membrane other than by polymerisation
  • H01M8/1088—Chemical modification, e.g. sulfonation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to compounds of the polyarylene sulfide-sulfonic acid class which have a good solubility in polar aprotic solvents, their use, and a process for the preparation of such polyarylene sulfide-sulfonic acids.
• Polyarylene sulfide in particular poly-p-phenylene sulfide, is known as a polymer which is distinguished by a particular resistance in respect of chemical and thermal influences.
• this polymer in order to be able to use this polymer for applications in aqueous media, it is expedient to increase its hydrophilicity.
• a method for achieving this aim by means of a sulfonation reaction is described in U.S. Pat. No. 4,110,265. In this method polyphenylene sulfide is reacted with oleum to give a sulfonated product which is employed as a cation exchanger material.
• the present invention was based on the object of providing a possibility, starting from customary polyarylene sulfides, of preparing polymers therefrom, by modification, which are soluble in polar aprotic solvents and which, for example, can easily be further processed to films.
• Another object comprises preparation of cation exchangers which are soluble in polar aprotic solvents starting from customary polyarylene sulfides.
• NMP N-methylpyrrolidone
• DMAC dimethylacetamide
• DMSO dimethyl sulfoxide
• DMF dimethylformamide
• Suitable polyarylene sulfides in the context of the present invention are generally polymers of which the main chain is formed from the recurring units of the form
• Ar in the formula is 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, biphenylene, naphthylene, anthrylene or another bivalent aromatic unit.
• the average molecular weights M w of suitable polyarylene sulfides are preferably in the range from 2000 to 200 000 g/mol.
• Poly-p-phenylene sulfide which has an average molecular weight M w of >50 000 g/mol and in which the aromatic unit is exclusively 1,4-phenylene, which can be detected by 1 H-NMR spectroscopy, is particularly preferably employed in the context of the present invention.
• poly-[1,4-phenylene sulfide]s which are crosslinked to a limited extent, but nevertheless are fusible and soluble, are used.
• the particularly preferred polyarylene sulfides have become known on the market under the brand names ®Fortron (Fortron Industries) or ®Ryton (Phillips Petroleum).
• a polyarylene sulfide-sulfonic acid in the context of the present invention is to be understood as meaning a polymer which is sulfonated to an extent of 0.1 to 100 mol %, preferably 2 to 40 mol %, based on the total amount of recurring units, i.e. the aromatic units carry sulfonic acid radicals (--SO 3 H).
• the aromatic units can be chlorinated to an extent of 0 to 40 mol %, preferably 5 to 25 mol %, based on the total amount of recurring units, and the sulfide bridges between the aromatic units can be oxidized to sulfoxide to an extent of 0 to 100 mol %, likewise based on the total amount of recurring units.
• the polyarylene sulfide-sulfonic acid according to the invention dissolves in N-methyl-pyrrolidone in an amount of more than 5% by weight, the soluble polyarylene sulfide-sulfonic acid having an average molecular weight of 2000 to 200 000 g/mol, preferably ⁇ 20 000 to 100 000 g/mol.
• the process for the preparation of the polyarylene sulfide-sulfonic acid according to the invention can be defined as chlorosulfonation of polyarylene sulfide.
• the polyarylene sulfide is first dissolved completely in chlorosulfonic acid to the extent of 5 to 15% by weight at a temperature in the range from -10 to +20° C., the solution is then stirred at reaction temperatures in the range from 5 to 20° C., if appropriate with the addition of oleum or acetic anhydride, and the product is then precipitated in an aqueous medium.
• the polyarylene sulfide is first dissolved completely not in pure chlorosulfonic acid but directly in a mixture of chlorosulfonic acid and oleum.
• chlorosulfonation in the context of the present invention is to be understood as meaning a one-pot reaction in which, in addition to the actual sulfonation of the aromatic units, oxidation of the sulfide bridges between the aromatic units to give sulfoxide takes place in part, and at the same time chlorination of the aromatic units also partly takes place.
• oleum or acetic anhydride is not absolutely essential in order to obtain a polyarylene sulfide-sulfonic acid which is soluble according to the invention, but if the chlorosulfonation reaction is assisted by the additives mentioned, the duration of the reaction may be shortened correspondingly, where appropriate. Furthermore, overall higher degrees of sulfonation are achieved at a given solubility.
• the amounts of oleum or acetic anhydride (Ac 2 O) added are usually 10 to 200% by weight of oleum, based on the weight of chlorosulfonic acid, or 5 to 30% by weight of acetic anhydride, likewise based on the weight of chlorosulfonic acid.
• the chlorosulfonated material is suspended in water and the suspension is boiled, so that the polyarylene sulfide-sulfonic acid chloride is converted into the polyarylene sulfide-sulfonic acid.
• This is also called sulfonated polyarylene sulfide below, and in addition to the sulfonic acid groups, can contain chlorine atoms bonded to the aromatic units and sulfoxide bridges.
• Solutions or dispersions in fluids preferably in polar aprotic solvents and in solutions of these solvents with water and aliphatic alcohols, can be prepared from the polyarylene sulfide-sulfonic acid.
• the oxidation state of the sulfide and sulfoxide bridges in the sulfonated polyarylene sulfide can be modified by the action of suitable oxidizing agents, for example H 2 O 2 , O 3 , HNO 3 and N 2 O 4 , so that the sulfoxide content is increased to 100 mol % or the sulfide and sulfoxide bridges are converted into sulfone groups (--SO 2 --) in an amount of up to 100 mol %.
• suitable oxidizing agents for example H 2 O 2 , O 3 , HNO 3 and N 2 O 4 , so that the sulfoxide content is increased to 100 mol % or the sulfide and sulfoxide bridges are converted into sulfone groups (--SO 2 --) in an amount of up to 100 mol %.
• suitable oxidizing agents for example H 2 O 2 , O 3 , HNO 3 and N 2 O 4
• the sulfonated polyarylene sulfide prepared by the process according to the invention and its oxidation products are outstandingly suitable for further processing to coatings, shaped articles, films or fibers.
• membranes which are distinguished by a proton conductivity in the range from 2 to 200 mS/cm, preferably from 5 to 50 mS/cm, can be produced from these.
• Such membranes are advantageously employed in electrolyte capacitors and in electrochemical cells, in particular in fuel cells and electrolysis cells.
• the electrolyte capacitors mentioned here are, in particular, structures called supercapacitors by the expert; these are electrolyte capacitors which have no electrically insulating layer between the electrode and electrolyte.
• Example 2 15 g of PPS as in Example 1 are dissolved in 300 ml of chlorosulfonic acid.
• the solution temperature, solution time, reaction temperature and reaction time can be seen from Table 1. After working up as in Example 1, a product of which the properties can be seen from Table 1 was obtained.
• a polymer obtained according to Example 2 is dissolved in N-methylpyrrolidone to the extent of 40% by weight, while heating.
• the solution which is liquid and clear even at 20° C., was spread out with a doctor blade to a film having a thickness of 100 ⁇ m and the film was dried at a temperature of 100° C. in a circulating air oven.
• a transparent flexible film on which the following measurements were made was formed in this manner:
• the ion exchange capacity is determined by dissolving 150 mg of product in 100 ml of DMSO and titrating the solution with NaOH solution (0.025 N in H 2 O/DMSO, 50% by volume of DMSO).
• the equivalence point is determined by a change in color of phenolphthalein or conductometrically.
• the alternating current conductivity is measured on membranes having a thickness of 60 to 100 ⁇ m which are contacted with the electrodes of a commercially available conductometer via 0.5% strength sulfuric acid. For pretreatment, the membranes were laid in water for one day. The alternating current conductivity was measured at 20° C. and a frequency of 1000 Hz.
• Example 5 15 g of PPS were dissolved in 300 ml of chlorosulfonic acid as in Example 5.
• the other reaction conditions are stated in Table 2, and working up was carried out as in Example 1 to give a pale yellow product of which the properties are listed in Table 2.
• An acid/base titration of a solution of the product from Example 6 gave an ion exchange capacity of 3.2 mmol/g.
• the polymer is amorphous to X-rays.
• the molar ratio of sulfide to sulfoxide bridges in the reaction product from Example 6 is 73 to 27, according to ESCA spectroscopy.
• the reaction product is suspended in 200 ml of a mixture of 30% H 2 O 2 and glacial acetic acid (mixing ratio of 1:1 volumes), the suspension is boiled for 30 minutes and filtered and the product is dried. Thereafter, the molar ratio of sulfide to sulfoxide bridges is 15 to 85.
• the reaction product is soluble in NMP to the extent of >20% by weight.
• the reaction product from Example 6 is gassed in a stream of ozone of 20 g of O 3 per m 3 for 15 minutes. Thereafter, no sulfide bridges and 22 mol % of sulfoxide bridges are to be detected by ESCA. The remainder are sulfone bridges, according to ESCA.
• the reaction product is soluble in NMP to the extent of >10% by weight.
• the chemical yield of the reactions in the abovementioned examples was more than 90%.

Landscapes

• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Electrochemistry (AREA)
• Sustainable Energy (AREA)
• Sustainable Development (AREA)
• Life Sciences & Earth Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Applications Claiming Priority (5)

Publications (1)

Family

ID=26017184

Family Applications (1)

Country Status (10)

Cited By (13)

Families Citing this family (8)

Citations (4)

• 1996
  • 1996-07-16 ES ES96926354T patent/ES2139376T3/es not_active Expired - Lifetime
  • 1996-07-16 JP JP50717397A patent/JP4081523B2/ja not_active Expired - Fee Related
  • 1996-07-16 WO PCT/EP1996/003118 patent/WO1997005191A1/de active IP Right Grant
  • 1996-07-16 US US08/983,626 patent/US6096856A/en not_active Expired - Fee Related
  • 1996-07-16 DE DE59603494T patent/DE59603494D1/de not_active Expired - Fee Related
  • 1996-07-16 DK DK96926354T patent/DK0840760T3/da active
  • 1996-07-16 EP EP96926354A patent/EP0840760B1/de not_active Expired - Lifetime
  • 1996-07-16 CA CA002227835A patent/CA2227835C/en not_active Expired - Fee Related
  • 1996-07-25 TW TW085109091A patent/TW438839B/zh not_active IP Right Cessation
• 1999
  • 1999-12-22 GR GR990403312T patent/GR3032225T3/el unknown

Patent Citations (4)

Non-Patent Citations (4)

Also Published As

Similar Documents

Legal Events